Chemical and Biomolecular Engineering - Research Publications

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    Pilot scale concentration of cheese whey by forward osmosis: A short-cut method for evaluating the effective pressure driving force
    Artemi, A ; Chen, GQ ; Kentish, SE ; Lee, J (Elsevier, 2020-11-01)
    Cheese whey was concentrated to a concentration factor of 2.7 in a pilot scale forward osmosis filtration system, using a commercial cellulose triacetate membrane in a spiral-wound configuration. The whey was concentrated in a batch mode, using sodium chloride as the draw solution at initial osmotic pressures of 53–75 bar. During the process, flux was shown to reduce due to the simultaneous decrease in the bulk osmotic pressure of the draw solution, increase in the bulk osmotic pressure of the whey and the effect of concentration polarisation on both sides of the membrane. The flux is known to be driven by the effective osmotic pressures of whey and the draw solution on the surface of the membrane active layer. A short-cut approach that requires minimal information in advance about the osmotic pressure of whey and the geometry of the filtration system was implemented, enabling the determination of these effective osmotic pressures. The results obtained were shown to be in agreement with the fundamental forward osmosis flux model. The short-cut approach can be utilised for estimating effective osmotic pressures of other liquid food streams to be concentrated by forward osmosis, without the need of external measurements.
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    The relevance of critical flux concept in the concentration of skim milk using forward osmosis and reverse osmosis
    Artemi, A ; Chen, GQ ; Kentish, SE ; Lee, J (Elsevier BV, 2020-10-01)
    Skim milk was concentrated at 10 °C using forward osmosis (FO), reverse osmosis (RO) and pressure-assisted forward osmosis (PAFO). A pressure of 40 bar, in the form of draw solution osmotic pressure (FO and PAFO modes) or transmembrane hydraulic pressure (RO mode) was applied; an additional hydraulic pressure of 2 bar was applied in the PAFO mode. More severe protein fouling was observed in RO, followed by PAFO and then FO. This was credited to the difference in the initial permeate flux, induced by the different effective driving pressures, with RO having a greater deviation of the initial flux from the critical flux value. The critical flux was determined for the FO and RO modes using a step-wise increase of draw solution osmotic pressure or hydraulic pressure, at a constant milk solids content. The critical flux was between 5.4 L/m2h (1.5 × 10−6 m3/m2s) and 7.2 L/m2h (2 × 10−6 m3/m2s) for both the FO and RO modes at a cross flow velocity of 0.2 m/s. The similarities in the critical flux for FO and RO suggests that the critical flux does not depend on the nature of pressure applied on the system (hydraulic or osmotic). Therefore, when operated at the same flux and crossflow velocity, FO would not fundamentally provide a lower fouling environment compared to RO. An increase of the solids content from 8.7% to 17.3% caused a reduction in the critical flux from 5.4 L/m2h to 3.1 L/m2h (8.5 × 10−7 m3/m2s).
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    Transforming salty whey into cleaning chemicals using electrodialysis with bipolar membranes
    Chen, X ; Chen, GQ ; Wang, Q ; Xu, T ; Kentish, SE (Elsevier, 2020-10-15)
    Large quantities of salty whey are produced during cheese manufacturing, posing an environmental problem. Here the feasibility of electrodialysis with bipolar membranes (EDBM) is evaluated for the first time as a mechanism to transform this saline effluent into sodium hydroxide and hydrochloric acid for reuse within the factory. This work also seeks to find the maximum acid and base concentration that can be achieved. For a pure sodium chloride solution, maximum acid/base concentrations of 3.6 ± 0.2 mol/L and 3.0 ± 0.3 mol/L are achieved using a stack of ten membranes including four bipolar membranes. The effects of proton leakage and water migration limit the generation of higher concentrations. The presence of calcium phosphate also has a negative effect on the EDBM performance, suggesting that pretreatment to remove this impurity is needed. In industrial practice, this pretreatment could be achieved by recycling around 9% of the base produced to precipitate these salts. The use of a partially cyclic operation allows 99% demineralization of pretreated salty whey, with high purity acid/base solutions of concentration near 3.5 mol/L. This work demonstrates EDBM as an effective process for transforming salty whey into chemicals for clean in place and ion exchange resin regeneration.
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    Sorption and diffusion of organic acid ions in anion exchange membranes: Acetate and lactate ions as a case study
    Wang, Q ; Chen, GQ ; Kentish, SE (Elsevier BV, 2020-11-15)
    In this study, the sorption behaviour and conductivity of two anion exchange membranes (AR103 and AR204) equilibrated with sodium acetate and sodium lactate solutions are studied across a range of concentrations and pH values. The results indicate that the dissociation equilibria of the organic acids differ between the membrane phase and the external solution. There are significant concentrations of the neutral organic acid in the membranes at pH 6.5 even though the dissociation is virtually complete in the external solution. The concentration of this neutral acid increases as the pH is lowered, leading to a reduction in membrane conductivity. The diffusion coefficients of acetate and lactate ions in these membranes are determined from conductivity data. The results show that these diffusion coefficients are relatively constant but decrease slightly with an increase of external solution concentration due to osmotic deswelling. The diffusion coefficient of the acetate anion decreases as the pH falls, possibly due to dimer formation. Models extended from Manning's condensation theory have been utilized in the prediction of the co-ion concentrations within the membrane and the diffusion coefficients of the lactate and acetate anions. There is an excellent agreement between the experimental values of these parameters and the model predictions for the sodium lactate system but the model is unable to accurately fit the sodium acetate data.
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    The application of forward osmosis to dairy processing
    Chen, GQ ; Gras, SL ; Kentish, SE (Elsevier, 2020-09-01)
    This work assesses the feasibility for concentrating process streams within dairy processing facilities using commercial forward osmosis membranes; to increase their total solids concentrations before entering energy intensive unit operations including thermal evaporators and spray dryers. These streams include demineralised whey, lactose, whey protein concentrate, sweet whey and skim milk. FTSH2O cellulose acetate (CTA) and Aquaporin flat sheet membranes are used with magnesium chloride concentrations of 1.66 ± 0.12 M as the draw solution. The experimental data are fitted to conventional mathematical models for forward osmosis, further modified by considering the nonlinear relationship between osmotic pressure and solute concentration. The diffusion coefficients of magnesium chloride in 1.6 M solutions at 10 °C, 20 °C and 50 °C are obtained and reported for the first time. Minimal fouling and a significantly smaller degree of concentration polarisation was observed on the membrane surface during lactose concentration compared to the concentration of other dairy solutions, due to the absence of proteins and calcium phosphate salts. The transfer of magnesium into the concentrated products was monitored and shown to be below 100 mg per 100 g dry powder. Acid cleaning alone was not effective in recovering pure water flux, and enzyme cleaners at neutral pH were needed given the limited pH tolerance (3–8) of the CTA membranes. Total solids concentrations of the concentrated dairy streams by forward osmosis (up to 40%) exceed those which can be achieved by nanofiltration and reverse osmosis (i.e., 15–20%). This study shows that forward osmosis is an effective approach to concentrate relevant dairy streams to achieve high concentration factors (e.g. >4 for sweet whey samples) without jeopardising product quality.
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    Pilot Study on the Removal of Lactic Acid and Minerals from Acid Whey Using Membrane Technology
    Talebi, S ; Suarez, F ; Chen, GQ ; Chen, X ; Bathurst, K ; Kentish, SE (American Chemical Society (ACS), 2020-02-24)
    Acid whey presents a major disposal issue for the dairy industry due to its high lactic acid and mineral concentrations. In this work, the feasibility of using membrane technology to treat acid whey to produce high quality whey powder was demonstrated at pilot scale. Three process combinations were tested, namely, (1) ultrafiltration and electrodialysis; (2) ultrafiltration, nanofiltration, and electrodialysis; and (3) ultrafiltration, dia-nanofiltration, and electrodialysis. All three combinations were successful in reducing the levels of lactic acid and minerals in acid whey. However, the lowest ratio between lactic acid and lactose (0.017 g lactic acid/g of lactose) was obtained with the process that utilized dia-nanofiltration. The energy required for the electrodialysis of the ultrafiltration permeate and dia-nanofiltration retentate were comparable (7.5 and 7.8 kWh/tonne of feed, respectively). However, the dia-nanofiltration retentate was at least 3.5 times more concentrated than the ultrafiltration permeate, thus reducing the annual energy consumption and capital investment of the electrodialysis unit. The product of the nanofiltration and electrodialysis process was successfully dried to produce a powder with an ash and moisture content of 4% and 2.5%, respectively.
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    Eutectic freeze crystallization of saline dairy effluent
    Chen, GQ ; Gras, SL ; Kentish, SE (Elsevier, 2020-04-15)
    The disposal of saline effluent in the dairy industry is subject to increasingly strict regulatory requirements. In this work, eutectic freeze crystallization (EFC) was investigated as a mechanism for the simultaneous separation of salts and ice in a typical saline effluent, namely salty whey. Experiments were conducted using salty whey samples collected from a dairy processing facility. The eutectic point of the salty whey was determined using differential scanning calorimetry and was found to be lower than that of NaCl solutions (−24 °C for salty whey vs. −21 °C for aqueous NaCl solutions). Crystallization experiments were then used to construct the phase diagram of this dairy stream under equilibrium conditions. The change in cation composition in the supernatant at the eutectic temperature was measured as a function of time and showed that pure NaCl salts and ice formed within 5 min after this temperature was reached. The energy consumption of this process was estimated to be ~120 kWh/t for salty whey, which is comparable to that for conventional thermal crystallization of brine.
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    Single and binary ion sorption equilibria of monovalent and divalent ions in commercial ion exchange membranes.
    Chen, GQ ; Wei, K ; Hassanvand, A ; Freeman, BD ; Kentish, SE (Elsevier, 2020-05-15)
    The co-ion and counter-ion sorption of monovalent (Na+, K+, Cl- and NO3-) and divalent ions (Ca2+ and SO42-) in commercial Neosepta ion exchange membranes were systemically studied in both single and binary salt systems. The new generation of Neosepta cation exchange membrane (CSE) showed a significant difference in water uptake and co-ion sorption compared to the earlier generation (CMX). Use of the Manning model confirmed that there were significant differences between these membranes, with the estimated value of the Manning parameter changing from 1.0 ± 0.1 for CMX to 2.8 ± 0.5 for CSE. There were fewer differences between the two Neosepta anion exchange membranes, AMX and ASE. In single salt solutions, potassium sorbed most strongly into the cation exchange membranes, but in binary salt mixtures, calcium dominated due to Donnan exclusion at low concentrations. While these trends were expected, the sorption behaviour in the anion exchange membranes was more complex. The water uptake of both AMX and ASE was shown to be the greatest in Na2SO4 solutions. This strong water uptake was reflected in strong sorption of sulphate ions in a single salt solution. Conversely, in a binary salt mixture with NaCl, sulphate sorption fell significantly at higher concentrations. This was possibly caused by ion pairing within the solution, as well as the strongly hydrophobic nature of styrene in the charged polymer. Water uptake was lowest in NaNO3 solutions, even though sorption of the nitrate ion was comparable to that of chloride in these single salt solutions. In the binary mixture, nitrate was absorbed more strongly than chloride. These results could be due to the low surface charge density of this ion allowing it to bond more strongly with the hydrophobic polymeric backbone at the exclusion of water and other ions.
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    Utilisation of salty whey ultrafiltration permeate with electrodialysis
    Talebi, S ; Kee, E ; Chen, GQ ; Bathurst, K ; Kentish, SE (Elsevier, 2019-12-01)
    Salty whey is a waste by-product that incurs increasingly high disposal costs for the dairy industry. This study investigated electrodialysis of the ultrafiltration permeate of salty whey as either a concentrate for the treatment of sweet whey or as a source of lactose and salt. The type of concentrate (0.1 m NaCl or salty whey permeate) did not affect the rate of sweet whey demineralisation or the energy consumed per tonne of whey, but less sodium and more divalent cations were removed when salty whey permeate was used as the concentrate. Salty whey permeate could be effectively demineralised using either 0.1 m NaCl or a second stream of salty whey permeate as the concentrate. The concentrate purity could be enhanced using monovalent selective membranes without increasing the energy consumption of the process (3.2 ± 0.3 kWh per kg of NaCl removed from the diluate at 15 V).
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    Preparation of Layer-by-Layer Nanofiltration Membranes by Dynamic Deposition and Crosslinking
    Liu, Y ; Chen, GQ ; Yang, X ; Deng, H (MDPI, 2019-02)
    In recent decades, the advancements in layer-by-layer (LBL) assembly technology have provoked increasing interest in the preparation of multilayer polyelectrolyte membranes with excellent performance. In the current study, a novel nanofiltration (NF) membrane was prepared by pressure-driven layer-by-layer (LBL) assembly of polyethylenimine (PEI) and polyacrylicacid (PAA) on a porous substrate with chemical crosslinking. The effect of deposition pressure on separation performance of the prepared membranes was studied. The surface morphology, hydrophilicity and the charge property of the dynamically-deposited membranes were compared with those prepared by static adsorption. The characterization results showed that dynamic deposition process resulted in a smoother membrane surface with improved hydrophilicity. The mechanism of water-path formation was proposed to interpret the effect of pressure on the membrane performance. Glutaraldehyde (GA) was used as a crosslinker to reduce the number of polyelectrolyte bilayers for obtaining good separation performance. The rejections of different inorganic salts of the dynamically-deposited NF membrane were also investigated.